(E)-methanediazoate | 64768-29-2

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: (E)-methanediazoate
• 英文别名: syn-Methyldiazotat；N-Nitrosomethylamine；N-methylnitrous amide
• CAS: 64768-29-2
• 化学式: CH₄N₂O
• 分子量: 60.0556
• InChiKey: CIJBKNZDKBKMFU-UHFFFAOYSA-N

物化性质

• 沸点：
  23.6±23.0 °C(Predicted)
• 密度：
  1.12±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.1
• 重原子数：
  4
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  41.5
• 氢给体数：
  1
• 氢受体数：
  3

ADMET

代谢

N-亚硝基甲基胺是已知的人体对乙基亚硝基甲胺和N-亚硝基二甲胺的代谢产物。

N-Nitrosomethylamine is a known human metabolite of ethylmethylnitrosamine and N-Nitrosodimethylamine.

来源:NORMAN Suspect List Exchange

反应信息

• 作为反应物：
  描述：

  (E)-methanediazoate 在 sodium perchlorate 作用下， 以 异丙醇 为溶剂， 生成 methanediazonium ion
  参考文献：
  名称：

  Rate-Limiting Formation of Diazonium Ions in the Aqueous Decomposition of Primary Alkanediazoates

  摘要：

  Rate constants, k(0), for the buffer-independent decomposition of four primary (E)-alkanediazoates and one primary (Z)-alkanediazoate in aqueous media at 25 degrees C, ionic strength 1 M (NaClO4) are reported. Between pH 4 and 12 the plot of log k(0) against pH is biphasic with a hydrogen ion-dependent reaction at the high-pH end changing to a pH-independent region at lower pH. The change in absorbance at 235 nm of the relatively stable (E)-trifluoroethanediazoate as a function of pH gives a good fit to a simple titration curve for a monofunctional acid with pK(a) = 7.00 +/- 0.04 that is in good agreement with the kinetic pK(a) determined from the pH-rate profile between pH 4 and 12. The plot of log k(1), the pH-independent rate constant, against sigma* for the primary (E)-alkanediazoates, and (E)-methane- and (E)-2-butanediazoates previously reported, yields a common line with a slope rho* = -4.4. Of the 1-butanol formed from the decomposition of (E)-1-butanediazoate in D2O at pH(obs),b, = 10.50, 6% contains deuterium, while, of the 1-butanol formed in the presence of 1 M NaOD in D2O, 25% contains deuterium. A total of 96% of the iodotrifluoroethane formed upon decomposition of (E)-trifluoroethanediazoate in a D2O solution that is 1 M in NaI contains at least a single deuterium atom. These data combined with small negative values of Delta S#, normal solvent deuterium isotope effects, and the decreases in k(1) of between 500- and 1000-fold on change of solvent to ethanol are consistent with a mechanism that involves the rate-limiting unassisted heterolytic bond fission of the diazoic acid to yield the diazonium ion. The decomposition of [O-16]-(E)-1-butanediazoate in water containing 47 +/- 2% O-18 yields 1-butanol of which 49 +/- 2% contains O-18. This observation, in combination with the observed pH-dependent deuterium incorporation into 1-butanol during decomposition of (E)-1-butanediazoate, above, indicates that the 1-butanediazonium ion is a diffusionally equilibrated intermediate. The rate constant for the pH-independent decomposition of the (Z)-trifluoroethanediazoate is 2600 times greater than that for the corresponding (E) isomer. The decomposition of the (Z)-trifluoroethanediazoate, but not its (E) isomer, is catalyzed by buffer acids, and the catalysis by carboxylic acids is characterized by a Bronsted plot with a slope alpha = 0.41. Catalysis by methoxylammonium ion is comparatively weak, the rate constant falling a log unit below the aforementioned Bronsted line. The solvent deuterium isotope effect for formic acid catalysis is k(HA)/k(DA) = 3.1 +/- 0.2 It is concluded that the mechanism for general acid catalysis of the decomposition of the (Z)-diazoic acid entails proton transfer to oxygen that is concerted with N-O bond heterolysis to yield the diazonium ion.

  DOI：

  10.1021/ja00094a016
• 作为产物：
  描述：

  1,3-二甲基脲 在 硫酸 、 硝酸 作用下， 以 二氯甲烷 为溶剂， 以86.9%的产率得到(E)-methanediazoate
  参考文献：
  名称：

  一种甲硝胺的制备方法

  摘要：

  本发明公开一种甲硝胺的制备方法，该法以N,N’‑二甲基脲为原料，包括如下步骤：(1)将N,N’‑二甲基脲的二氯甲烷溶液，缓慢加入到硝硫混酸中进行硝化反应，加料完毕后，反应混合物倒入冰水中，分离出有机相，水相用二氯甲烷萃取，合并有机相，依次用5％碳酸钠水溶液、蒸馏水洗涤，得到N,N’‑二甲基‑N,N’‑二硝基脲的二氯甲烷溶液；(2)将无机酸水溶液加入反应瓶中，加热至沸腾，开始滴加上述(1)中得到的N,N’‑二甲基‑N,N’‑二硝基脲的二氯甲烷溶液进行水解反应，滴加完毕后，保温30min，停止加热，水解液用二氯甲烷萃取，萃取液用无水硫酸镁干燥后，经浓缩得甲硝胺。本发明是为了解决甲硝胺制备过程中N,N’‑二甲基‑N,N’‑二硝基脲水解不充分、收率低等问题。主要用于甲硝胺的制备。

  公开号：

  CN108440336B

文献信息

• 一种甲硝胺的合成方法
  申请人：西安近代化学研究所

  公开号：CN108440335B

  公开（公告）日：2021-02-26

  本发明公开一种甲硝胺的合成方法，该法以N,N’‑二甲基脲为原料，包括如下步骤：(1)将N,N’‑二甲基脲溶于二氯甲烷配制成溶液，缓慢加入到硝硫混酸中进行硝化反应，反应温度‑5℃～0℃，加料完毕后，反应混合物倒入冰水中稀释；(2)将上述(1)中得到的稀释液升温至5℃～30℃进行水解反应，水解时间30min～120min，反应终止后，水解液相分离，二氯甲烷相用无水硫酸镁干燥后，经浓缩得甲硝胺。本发明是为了解决甲硝胺制备过程中反应操作步骤复杂、水解条件苛刻、收率低等问题。主要用于甲硝胺的制备。
• Decomposition of<i>N</i>′-Benzoyl-<i>N</i>-nitrosoureas in Aqueous Media
  作者：Celia Faustino、Luis García-Río、José Ramón Leis、Fátima Norberto

  DOI：10.1002/ejoc.200400537

  日期：2005.1

  The decomposition of N′-benzoyl-N-methyl-N-nitrosourea (BMNU) in aqueous media over the 0−14 pH range has been studied. In basic and neutral media (6 < pH < 14) the reaction proceeds through abstraction of the acidic proton of BMNU (pKa = 7.8) and subsequent decomposition of the conjugate base of the thus formed nitrosourea, via an intermediate benzoyl isocyanate. Support for this mechanism is provided

  已经研究了 N'-苯甲酰基-N-甲基-N-亚硝基脲 (BMNU) 在 0-14 pH 范围内在水性介质中的分解。在碱性和中性介质 (6 < pH < 14) 中，反应通过提取 BMNU 的酸性质子 (pKa = 7.8) 和随后通过中间体异氰酸苯甲酰酯分解由此形成的亚硝基脲的共轭碱进行。最终反应混合物中存在 N,N'-二苯甲酰脲支持这种机制，这是由于异氰酸苯甲酰酯被前者水解产生的苯甲酰胺捕获的结果。BMNU 的水解通过三种竞争途径发生：BMNU 共轭碱的自发分解，以及缓冲液催化和氢氧根离子催化的水加成到去质子化亚硝基脲的羰基上。N'-苯甲酰-N，N'-二甲基-N-亚硝基脲 (BDMNU) 是一种苯甲酰基亚硝基脲，缺乏 BMNU 的酸质子，在碱性介质中通过氢氧根离子对尿素羰基的攻击而水解。在酸性介质 (0 < pH < 6) 中，BMNU 仅产生脱氨基产物，这与其他 N-亚硝基化合物和等排亚
• Neurath,G. et al., Chemische Berichte, 1964, vol. 97, p. 1631 - 1638
  作者：Neurath,G. et al.

  DOI：——

  日期：——
• Castro, Albino; Leis, J. Ramon; Pena, M. Elena, Journal of the Chemical Society. Perkin transactions II, 1989, p. 1861 - 1866
  作者：Castro, Albino、Leis, J. Ramon、Pena, M. Elena

  DOI：——

  日期：——